Catalytic device.



%AE% PATNT FFJIQE.

JAMES DEWAR, OF LONDON, AND ADOLF LIEBMANN, OF WEYBRIDGE, ENGLAND, ASSIGNORS TO THE PROCTER AND GAMBLE COMPANY, OF CINCINNATI, OHIO, A

CORPORATION OF OHIO.

No Drawing.

To all whom it may concern:

Be it known that we, JAMES Dnwan, LL.

D., residing at 21 Albemarle street, in the county of London, England, and ADOLF LIEBMANN, Ph. 1)., re'sidmg at The Whim, Weybridge, in the county of Surrey, England, both subjects of the King of Great Britain, have invented new and useful Catalytic Devices, ofwhich the following is a specification. a The hydrogenation of fats, or oils, is, according to the present practice, effected by passing hydrogen through a mixture of liquid unsaturated fats, or oils, in the presence of a catalyst, either alone, or on an inorganic support. This process always involves the tedious operation of filtration, or some other method of deposition of the material in suspension, in order to separate the product of the reaction, and to recover the catalyst.

We have now found that this operation of filtration, or deposition, can be dispensed with, if the catalyst is distributed over a substance of a fibrous, or cohesive, character, or over yarns, or fabrics, made therefrom or over yarns, or fabrics, made from mixtures of different fibrous, or cohesive, materials, and the fibrous, or cohesive, substances, or the yarns, or fabrics, made therefrom, or the yarns, or fabrics, made from mixtures of different fibrous, or cohesive, materials, are so arranged as to prevent their disintegration.

The fibrous material hitherto most generally used as a support for catalysts is asbestos, but the fibers of this material are so Weak that, in the processes for hydrogenation already known, they very easily become disintegrated, which causes the suspension of the material in the liquid, necessitating subsequent filtration.

We have further found that organic fibrous materials can be used over which the catalyst is distributed, either in the fibrous condition, or in the form of yarns, or fabrics, made therefrom. We have found, for example, that cellulose, (such as cotton,

hemp, flax, jute) wool, silk, and similar sub-' stances, are suitable natural organic fibrous materials, but we do not limit ourselves to these groups, and we find that artificial fibrous materials, for instance, artificial silk, (if made by the viscose process, freed from sulfur) are also suitable.

CATALYTIC DEVICE.

Specification of Letters Patent. Pmtentcadl Apr. 117, 191?. Application filed June 16, 1915. Serial No. 34,506.

Other coherent materials to which the catalytic substances will adhere may he used, for instance, sponge.

If, according to our invention, the catalyst is, or the compounds from which the catalyst is formed in the process of hydrogenation, are, distributed over a fibrous raw material, it, or they, may, in order to prevent disintegration, for instance, be inclosed between two sheets of wire gauze, or other suitable material, or be otherwise fixed, for instance with wires, or threads. The said sheets, or the otherwise fixed fibrous material, may be stationary, because of the active movement of the liquid fat, or movable, as, for instance, by attaching them to an agitator.

If the catalyst is distributed over yarns, or fabrics, the yarns, or fabrics, may for instance be wound around frames, or other supports, which may be either stationary, or which may be fixed to an agitator, or they may even be Wound around the blades of an agitator.

It is even possible, according to our invention, if strongly cohesive fibrous materials (such as cotton,silk, or flax, or yarns, or fabrics, made therefrom) are used, to dispense with their being attached to any rigid frame either fixed or movable, thereby leaving them free to move in the liquid, but in this case the product resulting from the hydrogenation is not so satisfactory.

In the case ofthe catalytic metals, nickel, cobalt, and copper, the oxids, or carbonates, may be distributed over the materials hereinbefore referred to, and reduced prior to the process of hydrogenation, or they may be reduced thereon during the process of hydrogenation.

The latter process will be most advantageously effected. with the mixed catalysts in accordance with our previous application for United States patent Serial No. 842,538. In the case of the catalytic metals belonging to the platinum group, the catalysts are distributed over the fibers as finely divided metals. This is effected in the well-known Way by impregnating the fibrous material with an aqueous solution of a platinum salt and passing the material so impregnated ihrough a hot alkaline solution of formaldeyde.

If hydrogenation of suitable fats or oils is carried out with catalysts in accordance with our present invention, the result of hydrogenation is a clear liquid when hot, practically free from impurities, which solidifies, when cold, into a much whiter product than the oil from which it is obmined, and it is in a large number of cases quite inodorous and innocuous.

We have found that as small a proportion as .06 to .1 per cent. of the catalyst, or catalysts, to theoil treated, gives excellent results, and it is remarkable that the same catalyst may be employed repeatedly, without the necessity of renewal. We do not limit ourselves, however, to thisproportion. According to our invention the process of hydrogenation is practically continuous in asmuch as on the completion of one operation the catalyst remains in the vessel and is immediately ready after the removal of the oil for use in a further operation. This repetition continues until the catalyst gets poisoned by traces of impurities in the oils used. I

The hydrogenation can be carried out at atmospheric, or at increased, pressure.

The following examples will serve to illustrate further the nature of this invention, which, however, isnot confined to these examples. The parts are by weight.

Example Unbleached cotton yarn was passed through an aqueous solution of nickel and copper nitrates, containing nickel and copper in the mixture in the proportion of 66 parts of nickel to 33 parts of copper, the strength of the solution being such that after squeezing to such an extent that 7 0 to 80 per cent. of liquid is retained, the yarn contains so much of the salts as corresponds to 4 per cent. of metallic contents. It was then passed through a Soda solution, washed with cold water until free from carbonate and dried.

A quantity of yarn containing .08 per cent. of metals in proportion to the oil used, was wound around a nickel wire-gauze cylinder, which was then immersed in cotton seed oil contained in an autoclave, provided with an agitator. Hydrogen was passed through the oil while it was being stirred, the autoclave was closed up, and heated to 180190 centigrade, and the pressure allowed to rise to between 9 to 10 atmospheres. After half an hour the operation was interrupted, and the cotton seed oil, which after being poured off was perfectly clear, solidified on cooling to a white mass of good color, having a melting point of 39 centigrade.

A fresh portion of cotton seed oil was then treated with the same catalyst in the same way. The result was again a white solid substance of good color having a melting point of 46 centigrade.

The same catalyst was used for a third portion of oil. The melting point of the white solid was, after treatment for three quarters of an hour, 52 centigrade.

A fourth portion of oil treated yielded, after three quarters of an hour, a white fat of a melting point of 48 centigrade.

A fifth portion of oil yielded, after half an hour, a white fat, having a melting point of 39 centigrade.

Example I I Nickel and copper carbonates were distributed over linen yarn as before described 1n Example I, and cotton seed oil was hydrogenated in the same way as described in Example Lwith a quantity of linen yarn; containing .08 per cent. of metals in proportion to the oil used.

After treatment for half an hour, the resulting product was a white solid of good color, melting at 48 centigrade.

Example 1H.

Silk yarn prepared as described in Example I, was wound around the plates of an agitator. The silk, on which the carbonates o the metals had been precipitated was first washed with water, then with very dilute nickel acetate solution, to remove any excess of sodium carbonate, and finally, again with water. On hydrogenating for one hour as described in Example I, with a quantity of catalyst in proportion of .06 per cent. to the oil used, the resulting product was at ordinary temperature a white solid of good color, melting at 50 centigrade.

Example IV.

Bleached artificial silk yarn, freed from sulfur, was treated as described in Example I, and wound around the blades of an agitator, and cotton seed oil was hydrogenated with a quantity containing .08 per cent. of metals in proportion to the oil used. After half an hours treatment the resulting product was a white solid at ordinary temperature, of good color, melting at 44 centigrade.

E sample V.

Asbestos cord was treated as described in Example I, and a quantity of it, containing .18 per cent. of metals in proportion to the oil used, was twisted around the blades of an agitator, and the oil was hydrogenated for half an hour, as described in Example I. The resulting product was a white solid at ordinary temperature, melting at 48 centigrade.

What we claim is- 1. For use in the hydrogenation of unsaturated fats or oils in presence of a catalyst, the combination of a support, and a fibrous material of organic origin attached thereto, said fibrous material impregnated with the catalyst.

naaaeoe 2. For use in the hydrogenation of unsaturated fats or oils in presence of a catalyst, the combination of a support mounted for rotation, and a fibrous material attached 5 to said revoluble support, said fibrous material impregnated with the catalyst.

3. For use in the hydrogenation of unsaturated fats or oilsin presence of a catalyst, the combination of a support mounted 10 for rotation, and a fibrous material of organic origin attachefi to saiei revoluble sup- 

